1. Field of the Invention
This invention relates to ketone-terminated polyoxyalkylene compounds. More particularly, this invention relates to monoketone, diketone and triketone derivatives prepared by a method whereby the terminal hydroxyl groups of polyoxyalkylene compounds are oxidized to ketone groups with a hypochlorite oxidant in the presence of concentrated acetic acid. The ketone-terminated derivatives are useful as intermediates for the preparation of a wide variety of products. For example, they may be reacted with amines to provide fuel additives or converted to carboxylic acids to provide surfactants or the ketone products of this invention may be reacted with an alkali metal bisulfite to form products with good surface active properties.
2. Prior Art
It is known to react secondary alcohols and primary benzyl and allyl alcohols to the corresponding ketones and aldehydes in the presence of an oxidant such as Cu(NO.sub.3).sub.2 or Zn(NO.sub.3).sub.2 supported on silica gel in the presence of an aliphatic hydrocarbon solvent or a chlorinated aliphatic hydrocarbon solvent as shown, for example, by a paper by Takeshi Nishiguchi and Fumi Asano entitled "Oxidation of Alcohols by Metallic Nitrates Supported on Silica Gel" (J. Org. Chem. 1989, 54, 1531-1535).
Barak et al., in a paper entitled "Selective Oxidation of Alcohols by a H.sub.2 O.sub.2 -RuCl.sub.3 System under Phase-Transfer Conditions" (J. Org. Chem., 1988, Vol. 43, pp. 3553-3555), discloses in part that secondary alcohols can be oxidized to ketones with one hundred percent selectivity when using hydrogen peroxide as the oxidizing agent.
A paper entitled "Fast and Selective Oxidation of Primary Alcohols to Aldehydes or to Carboxylic Acids and of Secondary Alcohols to Ketones Mediated by Oxoammonium Salts under Two-Phase Conditions" by Anelli et al. (J. Org. Chem., 1987, Vol. 52, pp. 2559-2562) discloses oxidation of a variety of alcohols in solution in methylene chloride with sodium hypochlorite.
In copending Sanderson et al., U.S. application Ser. No. 07/444211, filed Dec. 1, 1989, and entitled "Ketone Derivatives of Polyoxypropylene Glycols", now U.S. Pat. No. 4,980,514, a process is disclosed wherein diketones are prepared by the oxidation of a polyoxypropylene glycol with an alkali metal or alkaline earth metal hypochlorite in the presence of a halogenated alkane solvent and a ruthenium catalyst.
In copending Sanderson et al., U.S. application Ser. No. 07/448428, filed Dec. 1, 1989, and entitled "Oxidation of Polyoxypropylene Glycols", now U.S. Pat. No. 4,978,785, a process is disclosed wherein carboxylic acid derivatives and methyl ketone derivatives of polyoxypropylene glycols are prepared by controlled nitric acid oxidation.
U.S. Pat. No. 4,141,919 discloses a process for producing alkoxy ketones by dehydrogenating an alkoxyalkanol in the presence of pre-activated copper-containing catalyst.